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|Title:||Dissociative electron transfer to diphenyl-substituted bicyclic endoperoxides : the effect of molecular structure on the reactivity of distonic radical anions and determination of thermochemical parameters|
|Authors:||Magri, David C.|
Workentin, Mark S.
|Citation:||Magri, D. C., & Workentin, M. S. (2014). Dissociative electron transfer to diphenyl-substituted bicyclic endoperoxides : the effect of molecular structure on the reactivity of distonic radical anions and determination of thermochemical parameters. Molecules, 19(8), 11999-12010.|
|Abstract:||The heterogeneous electron transfer reduction of the bicyclic endoperoxide 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]hept-5-ene (4) was investigated in N,N-dimethylformamide at a glassy carbon electrode. The endoperoxide reacts by a concerted dissociative ET mechanism resulting in reduction of the O-O bond with an observed peak potential of −1.4 V at 0.2 V s−1. The major product (90% yield) resulting from the heterogeneous bulk electrolysis of 4 at −1.4 V with a rotating disk glassy carbon electrode is 1,4-diphenyl-cyclopent-2-ene-cis-1,3-diol with a consumption of 1.73 electrons per mole. In contrast, 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (1), undergoes a two-electron reduction mechanism in quantitative yield. This difference in product yield between 1 and 4 is suggestive of a radical-anion mechanism, as observed with 1,4-diphenyl-2,3-dioxabicyclo-[2.2.2] octane (2) and 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]heptane (3). Convolution potential sweep voltammetry is used to determine unknown thermochemical parameters of 4, including the O-O bond dissociation energy and the standard reduction potential and a comparison is made to the previously studied bicyclic endoperoxides 1–3 with respect to the effect of molecular structure on the reactivity of distonic radical anions.|
|Appears in Collections:||Scholarly Works - FacSciChe|
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